Cleansing compositions adapted to inhibit the formation of body odor



United States Patent Office 3,355,388 Patented Nov. 28, 1967 3,355,388CLEANSING (:(BMPOSHTIONS ADAPTED T 1N- HIBIT THE FORMATION OF BODY ODORKenneth S. Karsten, Westport, Conn, assignor to R. T.

Vanderbiit ('10., inc, New York, N.Y., a corporation of New York NoDrawing. Filed Apr. 7, 1967, er. No. 629,115

5 Claims. (Cl. 252-107) ABSTRACT (BF THE DISCLOSURE This inventionrelates to a cleansing composition for inhibiting the formation of bodyodors. It comprises as the detergent base one or more water solubletoilet soaps, anionic detergents or nonionic detergents, and, asodorinhibiting constituents, an effective amount, about 1% to 4%, of askin-substantive antioxidant, optionally used together with about 0.1%to about 3% of a skin-substantive bacteriostat. Such antioxidantsinclude styrenated phenols, tri-alkylated phenyl phosphites,2,2'-ditertiary butyl-4,4'- isopropylidene diphenol (paraintermediate-alkyl phenyl) phosphites, and 2,2-methylenebis[6-(1-methylcyclohexyl)-para-cresol]. Such bacteriostats includebithionol, metal salts of bithionol, hexachlorophene, the zinc salt of1-hydroxy-Z-pyridinethione, tribromosalicylanilide, andtrichlorocarbanilide.

This application is a continuation-in-part of currently copendingapplication Serial No. 462,728 filed June 9, 1965, now abandoned, whichin turn was copending with and is a continuation-in-part of applicationSerial No. 321,799, filed November 6, 1963, now abandoned.

The elimination of human body odor has long been an objective in thefield of proprietary medicine. The prevailing theories on the causes ofhuman body odor are based on the underlying assumption that body odor iscaused by the secretion of perspiration. Thus, if perspiration isminimized, the formation of odors is inhibited. Accordingly, there arecurrently available deodorants which, in effect, are antiperspirants.These products usually embody aluminum compounds and are generallyapplied to the axillary regions of the body. The aluminum compounds actas astringents and thereby reduce perspiration in the regions whereapplied.

A more sophisticated approach to the problem has taken the form ofembodying bacteriostats in water soluble soaps and detergentcompositions intended for use in cleansing the body. Skin-substantivebacteriostats are chosen so that the bacteriostat remains on the surfaceof the body for a period of time subsequent to the use of soap ordetergent. This type of product has been developed because of the theorythat body odor is not due simply to the presence of the perspiration,but rather that body odor is caused by bacteria on the skin which breakdown the perspiration and natural body oils into odoriferous products.Thus, the presence of a bacteriostat on the skin is expected to reducethe multiplication and growth of bacteria and thereby inhibit theundesirable action of the bacteria on the perspiration. That this theoryis at least partially correct is proven by the success in reducing bodyodors by the use of a soap or detergent composition embodying askin-substantive bacteriostat. However, that such theory does notentirely explain the phenomenon of body odor formation is indicated bythe fact that even a drastic (99%) reduction in skin bacterialpopulation as a result of using a bacteriostat-containing soap stilldoes not eliminate the subsequent formation of odor. Therefore, improvedand alternative cleansing compositions are still desirable.

Accordingly, it is an object of this invention to provide an improvedcomposition for inhibiting body odor.

It is a further object of this invention to provide a cleansingcomposition for inhibiting body odor which embodies an antioxidant.

Another object of the present invention is to provide a cleansingcomposition for inhibiting body odor which embodies a combination of anantioxidant and a bacteriostat.

Briefly stated, one embodiment of the present invention is a compositioncomprising a water soluble soap and/or an anionic or nonionic detergent,and a skin-substantive antioxidant in an amount of at least about 1% byweight and sufiicient to inhibit the formation of body odor followingthe cleansing of the body with such composition.

Another embodiment of the present invention is a composition comp-risinga water soluble soap and/or an anionic or nonionic detergent, and acombination of an active proportion of a skin-substantive antioxidantand an active proportion of a skin-substantive bacteriostat, wherein theantioxidant and bacteriostat retain their activities andskin-substantivities in the composition.

It has been discovered that the presence of a skinsubstantiveantioxidant in such composition provides body odor inhibition when thecomposition is used to cleanse the human body. As indicated above,heretofore the prevailing theory of body odor prevention was that odorcould be prevented by eliminating or minimizing the presence of bacteriaon the surface of the skin. It was believed that these bacteria wereresponsible for convetting body perspiration and body oils intoodoriferous products.

The unexpected property of skin-substantive antioxidants in reducingbody odor does not appear to be the result of anti-bacterial action.Instead, it is theorized that the antioxidant functions to preventoxidation of the perspiration and body oils into odoriferous products.Thus, it would appear that an entirely new approach is provided foreliminating body odor.

The unique property of the skin-substantive antioxidants contemplated bythis invention suggests their use in combinations with skin-substantivebacteriostats which, when used alone, do not provide adequate deodorantaction. Thus, a two-pronged eifect is obtained by the use of suchcombinations-the bacteriostat serves to inhibit multiplication ofbacteria and thereby aids in preventing odor formation by minimizing oreliminating the odor causing element, and the skin-substantiveantioxidant serves to prevent body odor by preventing oxidativebreakdown of perspiration and natural body oils into odoriferousmaterials.

The eifectiveness of such compositions comprising an antioxidant aloneor in' combination with a bacteriostat to inhibit the formation of bodyodors following the cleansing of the body with such compositions hasbeen demonstrated in clinical tests. Such clinical tests were conductedusing bars of Ivory brand (Reg. T.M., Procter & Gamble Co.) soap, whichis a neutral white, high grade toilet soap comprising a mixture of 80%sodium soap and 20% potassium soap derived from a blend of tallow and30% coconut oil-glyceride blend (made in ac cordanoe with US. Patent No.2,295,594). The soap bars used in such tests had incorporated thereinadditives of the character and amounts set forth below:

Table I Soap Formulation Antioxidant Bacteriostat Code None None.Styrenated phenols 2%. Do. Styrenated phenols 4% Do. None Sodiumbithionolate 2%. E Styrenated phenols 4% D0.

The mixture of styrenated phenols referred to in Table I is furthercharacterized hereinafter in connection with the structural formula forsuch phenols.

The test soaps were evaluated in pairs, each subject person using onetest soap on one axillary area and a second test soap on the otheraxillary area. This method of testing eliminates differences in exposureto contamination, diet, illness or exercise which might be encounteredwhen soaps are tested on two different individuals. The scores of thenine or more persons in each test were averaged for reporting.

The clinical testing was conducted as follows. The subjects were givensoap formulation A, the control soap, and were instructed to use thissoap for all bathing for a preliminary period of approximately fivedays.

Next, each subject underwent a first supervised wash with soapformulation A, the control soap. In such supervised wash, a wet six-inchsquare of new white terry cloth was rubbed on a bar of the control soapfor about fifteen seconds. This cloth was then used to scrub oneaxillary area for a period of about one minute. A fresh terry clothsqu'are was then used to wipe away the lather and the area was driedwith a disposable towel. The procedure was repeated for the otheraxillary area. Such supervised washings were under the direction of askilled technician who had the additional responsibility of assuringthat the proper soap formulation was used.

Twenty-four hours following the supervised wash as described above, eachaxilla of each subject was evaluated for axillary odor and the averageof the scores in each group of subjects was recorded. No interveningwashes were permitted during this twenty-four hour period. The odor wasevaluated by two judges using a rating scale ranging from zero,indicating no detectable body odor, up to ten indicating a very strongand disagreeable body odor. This evaluation technique was usedthroughout the clinical tests. The odor rating of the two axillae ofeach subject was separately noted so that subsequent comparison testratings could be weighted to compensate for any differences between theaxillae of a subject.

For the next three days, each of the subjects bathed with soapformulation A, the control soap.

On the next two succeeding days, the fifth and sixth days following theinitial supervised wash, there were supervised washes at about 7 a.m.and 4 p.m. During these two days of supervised washes, one soapformulation was used for one axilla of a subject and a second soapformulation was used for the other axilla of the same subject.

On the seventh day, there was a supervised wash at about 7 am, with theaxillae of each subject being bathed with the soap formulations in themanner utilized on the fifth and sixth days. At 4 p.m. on the seventhday, nine hours after the supervised wash, the subject was evaluated forodor by the judges, utilizing the rating scale set forth above. Eachaxillary area was separately rated and the rating noted. Following theabove odor rating, there was a final supervised wash again using thesame soap formulations as used previously.

A final odor evaluation was made on the eighth day, about twenty-fourhours after the final supervised wash.

The subjects were instructed not to smoke or eat for at least one hourprior to those supervised washes which were followed immediately by anodor evaluation. The subjects were instructed not to use any shavinglotion or the like on such days. During the entire period of the tests,the subjects were instructed to use no anti-perspirants or deodorants.Other than these restrictions, the subjects were permitted their normaldaily activity and personal hygiene.

The odor evaluations were analyzed as follows: First, arithmeticaverages were computed based on the numerical evaluations of the judgesscores on each of the nine or more subjects using the soaps referred toin Table I. Then the differentials were computed between the initialodor evaluation and the evaluations on the seventh day, nine hours aftera supervised wash, and on the eighth day, 24 hours after the finalsupervised wash. The standard deviation (normally represented by sigma,a) was determined statistically to be 0.06. The aforesaid differentialswere then divided by 2 sigma and the resulting quotients tabulated inTable II. In such table, any positive number represents a reduction inodor, and any number of unity or greater indicates a statisticallysignificant result at the confidence level.

Analyzing the data in Table II, it can be seen that the use of 2%styrenated phenols in formulation B results in an odor improvement overthat provided by the control soap, formulation A. However, increasingthe amount of styrenated phenols to 4% in soap formulation C resulted ina decrease in deodorant effectiveness, as shown by a comparison offormulations A and C. It is believed that this adverse result is causedby the residual odor of the antioxidant itself. Of course, it is to beappreciated that the odor of the antioxidant must be taken into accountin odor evaluation ratings since the ultimate objective is to providecomplete absence of any odor.

In the comparison of formulations A and D, the expected deodorantadvantage of the use of the skinsubstantive sodium bithionolate isevidenced.

In the list of the camparisons involving the control formulation as oneof the soaps, it can be seen that the combination of antioxidant andbacteriostat of formulation E is a substantial improvement over thecontrol, in the evaluation conducted after the sixth day wash.

The last three comparisons in Table II involve the rating of one testsoap formulation as against another. In the comparison of formulations Cand D, formulation D is indicated to be superior. This may be attributedto the odor of the antioxidant itself, as was evident from a comparisonof soap formulations A and C.

The comparison of formulations D and E indicate that there is anadvantage in the addition of an antioxidant to the bacteriostat.

Likewise, the advantage shown by formulation E over that of formulationD also shows that the combination of an antioxidant with a bacteriostatis superior to the antioxidant alone.

In view of the improvement of 2% of the antioxidant formulation B overthat of the 4% antioxidant formulation C, it is evident that acombination of 2% styrenated phenols and 2% sodium bithionolate wouldrepresent a substantial improvement in deodorant properties over any ofthe other combinations tested.

In another test, in which a soap formulation containing 1% styrenatedphenols was compared with control soap formulation A, it was determinedthat there was no odor improvement. A level of 1% of this antioxidantwas insufficient to improve odor.

Anionic or nonionic detergents may be substituted effectively for partor all of the toilet soap used in the foregoing description.

The following test is suitable for use in determining theskin-substantivity.

A button of animal hide is soaked for five minutes in an 8% aqueoussolution of a neutral high grade white toilet soap or of an anionic ornonionic detergent, having incorporated therein 1% by weight of the soapor detergent of the constituent being tested, e.g., a bacteriostatand/or an antioxidant. The hide button is then rinsed four times withdistilled water.

A tryptone glucose yeast agar is seeded with an 18- hour nutrient brothculture of a bacterium such as Escherichia coli, Staphylococcus aureus,Bacillus subtilis or Salmonella typhosa at the rate of 20 milliliters ofthe broth culture per liter of agar. The agar solution comprises perliter, grams of tryptone, 2.5 grams of yeast extract, 1 gram of glucose,15 grams of agar and sufficient water to make one liter. A sufficientamount of the indicator 2,3,5-triphenyl ZH-tetrazolium is then added toachieve a 0.1% concentration of the latter in the seeded culture.Thereafter, the seeded agar is added to a sterile Petri dish and allowedto harden.

The button of animal hide is then placed on the hardened agar andsufiicient of the above described seeded agar is added to completelycover the hide button. The Petri dish containing the hide button is thenincubated at about 37 C. for about 18 hours. At this time, the cultureis observed to determine the presence or absence of the formation ofcolor in the media surrounding the button. The absence of colorindicates that the antioxidant was skin-substantive to the hide button.

The foregoing test depends on the sensitivity of the indicator in thepresence of oxygen released by certain growing bacteria. A red colorexhibited by the indicator indicates the presence of such oxygen. If anymeasurable antioxidant is present in the vicinity of the hide button, itprevents absorption by the indicator of the small amount of oxygenreleased by the bacteria and in this area there will be no colorformation.

Using the foregoing test, it has been determined that the styrenatedphenols referred to herein were skin-substantive in neutral white toiletsoap and in anionic and nonionic detergents, such as sodium laurylsulfate, doclecyl-benzene sodium sulfonate and octyl phenoxy polyethoxyethanol. In addition, other phenol-type antioxidants found to beskin-substantive in such soaps and detergent include2,2'-ditertiary-butyl-4,4' isopropylidene diphenol (para-nonyl or octylphenyl) phosphites, trialkylated phenyl phosphites, and2,2'-methylenebis [6-(1- methylcyclohexyl -para-cresol] In addition tothe sodium bithionolate utilized in the odor evaluating tests set forthabove, other skinsubstantive bacteriostats are suitable for use in thepresent invention in combination with a skin-substantive antioxidant.Such skin-substantive bacteriostats include, for example, bithionol,other metal salts of bithionol, such as zinc bithionolate,hexachlorophene, the Zinc salt of lhydroxy-2-pyridinethione,tribomosalicylanilide and trichlorocarbanilide.

The amount of the bacteriostats used in the compositions of the presentinvention may be from about by weight to 3% and preferably from about/2% to 2%. The lower limit in this respect is set by the fact that atleast this minimum is necessary in achieving antibacterial action. Theupper limit is not critical, although effectiveness is notproportionately increased with increased concentrations above about 3%.

As indicated by the test results set forth above, it is seen that anamount greater than about 1% by Weight of antioxidant is necessary incompositions of the present invention. According to the data,concentrations of about 2% are preferred. It can be seen that 4%represents a practical upper limit in view of the problem encountered ofthe undesirable odor of the antioxidant itself. When used incombination, it is desirable to use about 2% of antioxidant and 2% ofbacteriostat.

The styrenated phenols referred to in Table I and utilized in the odorevaluation tests set forth above was a 6 mixture of mono-, di-, andtri-styrenated phenols, the formula for which is set forth below:

acs

where n is an integer from 1 to 3, inclusive. Such a mixture is sold asAgeRite Spar (Reg. T.M., the B. F. Goodrich Company) and comprises about15% mono-,

55% di-, and 30 tri-styrenated phenols. Kehes U.S..

Patent No. 2,670,340 describes at col. 1, lines 45 et seq.

a process of making such mixtures of styrenated phenols.

The tri-[(intermediate-alkyl) phenyl] phosphites referred to herein havethe general structure:

wherein R is an intermediate-length alkyl radical, e.g., heptyl, octyl,nonyl or decyl. Trinonylated phenyl phosphites are preferred. Mixturesof tri-alkylated phenyl phosphites may be used.

The 2,2'-ditertiary butyl-4,4-isopropylidene diphenol (paraintermediate-alkyl phenyl) phosphites as referred to herein have thestructure:

' x and y will be fractional numbers intermediate between 1 and 2.Illustrative examples of such phosphites include (2,2' ditertiary-butyl-4,4'-isopropylidenedjphenol)bis (p-octylphenyl)phosphite, bis(2,2-di-tertiary-butyl-4,4- isopropylidenediphenol)(p-octylphenyl) phosphite and their mixtures, and(2,2'-di-tertiary-butyl-4,4-isopropylidenediphenol) bis (p-nonylphenylphosphite, bis (2,2-ditertiary butyl 4,4 isopropylidenediphenol)(p-nonylphenyl) phosphite and their mixtures.

The structure of 2,2-methylenebis [6-(l-methylcyclohexyl)-para-cresol]is:

OH HO CH3! i CH3 y co l CH3 CH3 Not all antioxidants areskin-substantive. For instance, ortho-tolyl biguanide (Sopanox, Reg.T.M., Monsanto Chemical Co.) is not. This compound is believed to be themost widely used antioxidant to prevent rancidity in toilet soaps. Whenso used, it comprises 0.04 to 0.1% of the soap. Also, 2,6-ditertiarybutyl-6-methyl phenol is not skin-substantive. Such phenol is referredto in Taylors U.S. Patent No. 2,977,316.

As used herein, soap refers to water-soluble alkali metal, ammonium, andamine soaps suitable for cleansing the human body, such as the sodium,potassium, ammonium, or triethanolamine salts of the higher fatty acidsderived from naturally occurring plant or animal fats or oils, such ascoconut oil, tallow, palm oil, lard, soybean oil, babassu oil, castoroil, whale or fish oils and the like, and mixtures thereof.

The term detengent refers to anionic and nonionic detergents suitablefor cleansing the body. Anionic detergents are generally derived fromfatty matters or their derivatives by sulfonation. Illustrative examplesinclude the sodium salts of sulfonation products of higher alcohols,e.g. sodium lauryl sulfate; sodium salts of alkyl aryl sulfonates, e.g.,dodecylbenzene sodium sulfonate; alkyl aryl snlfonates; the product ofchlorosulfonation of paraffin hydrocarbons, e.g., octadecenyl sulfonate;and the condensate of a fatty acid chloride with an amine.

Nonionic detergents include surface active agents which do not formions, such as those obtained by condensation of ethylene oxide withfatty substances and their derivatives. Illustrative examples ofnonionic detergents include the condensation products of propyleneglycol (mol. wt. 900) with fatty acid derivatives; the condensationproducts of ethylene oxide with fatty alcohols such as lauryl alcohol;the condensation products of fatty acids with diethanolamine; thecondensation products of ethylene oxide with alkyl phenols; and fattyacid cyclo-imides.

The cleansing compositions to which this invention is directed consistessentially of one or more of such soaps or such detergents or mixturesthereof as the predominant cleansing constituents, such being referredto herein as the detergent base; the skin-substantive antioxidants,optionally together with skin-substantive bacteriostats, as hereindescribed; and optionally other conventional constituents of cleansingcompositions, such as, by way of illustration, emollients, fillers, mildabrasives, neutral salts, perfumes or a major proportion of solvent, andwhich are used in amounts which do not materially affeet in an adversemanner the body-odor inhibiting characteristics of the totalcomposition.

The compositions may be prepared as pastes, bars, liquids (e.g.,shampoos), flakes or granules.

The specific embodiments described herein are intended as merelyillustrative of the present invention and variations may be made thereinby one skilled in the art without departing from the spirit and scope ofthe invention.

What is claimed is:

1. A composition consisting essentially of a detergent base selectedfrom the class consisting of at least one of water soluble soaps,nonionic detergents, anionic detergents and mixtures thereof, and askin-substantive antioxidant selected from the class consisting ofmono-, di-, and tri-styrenated phenols, tri-[(intermediate-alkyl)phenyl] phosphites, 2,2'ditertiary buty1-4,4'-isopropylidene diphenol(para intermediate-alkyl phenyl) phosphites, and 2,2'-methylenebis[6-(1-methyl-cyclohexyl)- para-cresol], said antioxidant being presentin said composition in an amount in the range of at least about 1% toabout 4% by weight and sufiicient to inhibit the formation of body odorfrom an area of the human body cleansed with said composition.

2. A composition in accordance with claim 1 wherein said detergent baseis a water soluble toilet soap and wherein said antioxidant is a mixtureof the styrenated phenols.

3. A composition in accordance with claim 1 wherein said detergent baseis an anionic detergent and said antioxidant is a trinonylated phenylphosphite.

4. A composition consisting essentially of a detergent base selectedfrom the class consisting of at least one of water soluble soaps,nonionic detergents, anionic detergents and mixtures thereof, askin-substantive antioxidant selected from the class consisting ofmono-, di-, and tristyrenated phenols, tri[(intermediate alkyl) phenyl]phosphites, 2,2'-ditertiary butyl-4,4-isopropylidene diphenol (paraintermediate-alkyl phenyl) phosphites, and 2,2-methylenebis[6-(l-methyl-cyclohexyl)-para-cresol], said antioxidant being present inan amount at least about 1% up to about 4% by weight, and askin-substantive bacteriostat selected from the class consisting ofbithionol, sodium or zinc salts of bithionol, hexachlorophene, the zincsalt of 1-hydroxy-2-pyridinethione, tribromosalicylanilide andtrichlorocarbanilide, and mixtures thereof, in an amount in the range offrom about to about 3%, said antioxidant and said bacteriostat retainingtheir respective activities and substantivities in said composition.

5. A composition in accordance with claim 4 wherein said detergent baseis a water soluble toilet soap, said bacteriostat is a sodium or zincsalt of bithionol and said antioxidant is a mixture of styrenatedphenols.

References Cited UNITED STATES PATENTS 1,987,288 1/1935 Brunson 260-39852,112,381 3/1938 Solyberg 252-404 2,234,379 3/1941 Martin 252-4042,467,295 4/1949 Cook 252-108 2,734,924 2/1956 Lambert 260-619 2,814,59711/1957 Wenneis et al. 252-107 2,977,316 3/1961 Taylor 252-107 3,024,1633/1962 Harvey et al. 252-106 3,152,039 10/1964 Mattson 252-107 3,172,8713/1965 Maly et al. 260-967 FOREIGN PATENTS 215,821 6/195'8 Australia.

792,538 3/1958 Great Britain.

671,117 9/1963 Canada.

LEON D. ROSDOL, Primary Examiner.

W. SCHULZ, Assistant Examiner.

1. A COMPOSITION CONSISTING ESSENTIALLY OF A DETERGENT BASE SELECTEDFROM THE CLASS CONSISTING OF AT LEAST ONE OF WATER SOLUBLE SOAPS,NOMIONIC DETERGENTS, ANIONIC DETERGENTS AND MIXTURES THEREOF, ANDSKIN-SUBSTANTIVE ANTIOXIDANT SELECTED FROM THE CLASS CONSISTING OFMONO-, DIAND TRI-STYRENATED PHENOLS, TRI((INTERMEDIATE-ALKYL) PHENYL)PHOSPHITES, 2,2''DITERTIARY BUTYL-4,4''-ISOPROPYLIDENE DIPHENOL (PARAINTERMEDIATE-ALKYL PHENYL) PHOSPHITES, AND 2,2''-METHYLENEBIS(6-(1-METHYL-CYCLOHEXYL) PARA-CRESOL), SAID ANTIOXIDANT BEING PRESENT INSAID COMPOSITION IN AN AMOUNT IN THE RANGE OF AT LEAST ABOUT 1% TO ABOUT4% BY WEIGHT AND SUFFICIENT TO INHIBIT THE FORMATION OF BODY ODOR FROMAN AREA OF THE HUMAN BODY CLEANSED WITH SAID COMPOSITION.